Method for the synthesis of amine-functionalized fullerenes involving set-promoted photoaddition reactions of -silylamines

Suk Hyun Lim, Jinju Yi, Gyeong Min Moon, Choon Sup Ra, Keepyung Nahm, Dae Won Cho, Kyungmok Kim, Tae Gyung Hyung, Ung Chan Yoon, Ga Ye Lee, Soojin Kim, Jinheung Kim, Patrick S. Mariano

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31 Scopus citations

Abstract

A novel method for the preparation of structurally diverse fullerene derivatives, which relies on the use of single electron transfer (SET)-promoted photochemical reactions between fullerene C60 and α-trimethylsilylamines, has been developed. Photoirradiation of 10% EtOH-toluene solutions containing C60 and α-silylamines leads to high-yielding, regioselective formation of 1,2-adducts that arise through a pathway in which sequential SET-desilylation occurs to generate α-amino and C60 anion radical pair intermediates, which undergo C-C bond formation. Protonation of generated α-aminofullerene anions gives rise to formation of monoaddition products that possess functionalized α-aminomethyl-substituted 1,2-dihydrofullerene structures. Observations made in this effort show that the use of EtOH in the solvent mixture is critical for efficient photoproduct formation. In contrast to typical thermal and photochemical strategies devised previously for the preparation of fullerene derivatives, the new photochemical approach takes place under mild conditions and does not require the use of excess amounts of substrates. Thus, the method developed in this study could broaden the scope of fullerene chemistry by providing a simple photochemical strategy for large-scale preparation of highly substituted fullerene derivatives. Finally, the α-aminomethyl-substituted 1,2-dihydrofullerene photoadducts are observed to undergo photoinduced fragmentation reactions to produce C60 and the corresponding N-methylamines.

Original languageEnglish
Pages (from-to)6946-6958
Number of pages13
JournalJournal of Organic Chemistry
Volume79
Issue number15
DOIs
StatePublished - Aug 2014

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